CN110214160A

CN110214160A - With improved carbon fiber-matrix interface polycarbonate

Info

Publication number: CN110214160A
Application number: CN201880008403.7A
Authority: CN
Inventors: 扬·亨克·坎普斯; 尼基尔·韦尔盖塞; 奈尔斯·罗森库斯特; 吕德·范·德·海登; 保罗·西贝特
Original assignee: SABIC Global Technologies BV
Current assignee: SABIC Global Technologies BV
Priority date: 2017-01-25
Filing date: 2018-01-25
Publication date: 2019-09-06
Anticipated expiration: 2038-01-25
Also published as: CN110214160B; EP3574045A1; WO2018138229A1; EP3574045B1; US20190359782A1; US11447611B2

Abstract

Disclosed various embodiments are related to composition.The present invention includes the component carbon fibers of polycarbonate component and the surface comprising activation.Interface can be formed between polycarbonate component and component carbon fibers.

Description

With improved carbon fiber-matrix interface polycarbonate

It is entitled " with the improved poly- carbonic acid of carbon fiber-matrix interface this application claims what is submitted on January 25th, 2017 The priority of the U.S. Provisional Patent Application Serial No. 62/450,208 of ester ", the disclosure of which are integrally incorporated by citation with it Herein.

Background technique

Composite material is formed by by polymer and reinforcing fiber and has reached desired balance between intensity and light weight, Keep them functional in numerous applications.The intensity of composite material depends on a variety of different factors.For example, the intensity of material can To depend on the connection being used to form between the material or those materials of composite material.In order to provide for broader applications Composite material, it is expected that generating the composite material with increased intensity.

Summary of the invention

By polymer and reinforcing fiber be formed by composite material be it is desired, wherein fiber, which has been shared, is applied to composite wood The external carbuncle of material.Strength levels of the intensity of composite material sometimes by interface between polymer and fiber are limited.For example, such as Fruit interface is fragile, it is meant that there is poor combination or connection between the polymer and reinforcing, then composite material is total strong Degree may undesirably change.

The intensity at interface between polymer and fiber can be improved in the modification of fiber.For example, by modification fiber surface or Person's modified polymer (for example, with can be with functional group of the functional group reactions of polymer), can be used as whole enhancing interface and Composite material.

In embodiments of the present invention, polycarbonate component and component carbon fibers include the surface of activation.It can be poly- Interface is formed between carbonate component and component carbon fibers.

It in yet another embodiment of the present invention, can be by the carbon on the surface comprising polycarbonate component and containing activation The composition of fibre fractionation forms composite material.The interface of composite material is included in the work of polycarbonate component and component carbon fibers The covalent bond formed between the surface of change.

In other embodiments of the present invention, the method for composite material is formed including that will include polycarbonate component and contain There is the composition of the component carbon fibers on the surface of activation to contact with mold.Method further includes heating mould and applies pressure to mold Power.

Detailed description of the invention

Attached drawing is usually by way of example rather than limiting the multiple realities for illustrating to discuss come by way of in document of the present invention Apply mode.

Fig. 1 shows the scanning electron micrograph (SEM) of composite material in some embodiments.

Fig. 2 is the amplification picture of composite material shown in FIG. 1.

Fig. 3 shows the SEM picture of composite material in some embodiments.

Fig. 4 is the amplification picture of composite material shown in Fig. 3.

Fig. 5 shows the SEM picture of composite material in some embodiments.

Fig. 6 is the amplification picture of composite material shown in fig. 5.

Specific embodiment

With detailed reference to the certain embodiments of disclosed theme, these embodiments are partially shown in the accompanying drawings Example.Although the theme that cited claim description will be combined disclosed, it should be understood that the theme illustrated not purport Claim is being limited to disclosed theme.

By polymer and reinforcing fiber be formed by composite material be it is desired, wherein fiber, which has been shared, is applied to composite wood The external carbuncle of material.Degree of the intensity of composite material sometimes by boundary strength between polymer and fiber is limited.For example, such as Fruit interface is fragile, it is meant that there is poor combination or connection between the polymer and reinforcing, then composite material is total strong Degree may undesirably change.

Various embodiments are related to the composition comprising polycarbonate component and component carbon fibers.Composition can be taken more Kind form, including composite material or cured composite material.Component carbon fibers may include the surface of activation.Component carbon fibers The surface of activation especially may include the nucleophilic group that can be reacted with polycarbonate component.It in the composite, can be poly- Interface is formed between carbonate component and component carbon fibers.It can be formed by the connection between polycarbonate component and carbon fiber Interface.Connection can be by chemical bond (such as covalent bond, ionic bond or hydrogen bond), physical connection (for example, Van der Waals force or machine Tool connection) and their combination realization.

The composition of various embodiments can have the component carbon fibers and polycarbonate component of any suitable amount.It takes Certainly in the concrete application of composition or desired property, the amount of every kind of component be can change.For example, component carbon fibers can be in group It closes in the range of the about 1wt% to about 70wt% of object perhaps in the range of the about 15wt% to about 60wt% of composition or group In the range of the about 30wt% to about 50wt% for closing object.Polycarbonate component can be in the about 1wt% to about 70wt% of composition In the range of perhaps in the range of the about 15wt% to about 60wt% of composition or the about 30wt% of composition is to about In the range of 50wt%.

In some embodiments, component carbon fibers and polycarbonate component are directly contacted in interface.In some examples In, interface can be formed by being formed by covalent bond between polycarbonate component and the surface of the activation of component carbon fibers. More specifically, covalent bond can between the surface of the activation of component carbon fibers and the electrophilic side chain of polycarbonate component shape At.There is provided herein the examples of the suitable electrophilic side chain of polycarbonate component.The electrophilic side chain of polycarbonate component and The degree that the surface of the activation of component carbon fibers bonds together can about 1% to about 100% or about 50% to about 100% or In the range of person about 75% to about 100%, electrophilic side chain can be covalently bound to the surface of the activation of component carbon fibers.

The higher percentage for being covalently bound to the electrophilic side chain on the surface of the activation of component carbon fibers can have increasing The effect of strong interface.However, the hundred of the electrophilic side chain on the surface with the lower activation for being covalently bound to component carbon fibers Divide than certain effects can also be assigned.For example, the electrophilic group not being bonded can be used for participating in it is other with polycarbonate component The intermolecular and intramolecular crosslinking of electrophilic group.This can be used as whole polycarbafil component.Relative in crosslinking Used electrophilic side group number, control be bonded to polycarbonate component activation surface electrophilic side group number Ability can lead to the control to composite properties.

It is opposite or in combination with covalent bond as described above, it can also be formed by various non-covalent physical connections poly- Interface between carbonate component and carbon fiber.For example, ionic bond combination polycarbonate component and carbon fiber can be passed through.Separately Outside, hydrogen bond can be formed between polycarbonate component and component carbon fibers.For example, can be in the electrophilic of polycarbonate component Hydrogen bond is formed between the surface of the activation of side chain and component carbon fibers.

In some instances, physical connection can connect component carbon fibers and polycarbonate component.For example, polycarbonate group May exist Van der Waals force between the surface of the activation of the electrophilic side chain and component carbon fibers that divide, forms boundary between them Face.In some instances, interface can be formed by the mechanical connection between polycarbonate component and component carbon fibers.For example, Polycarbonate component can wind around component carbon fibers.Polycarbonate component can be completely wound around carbon fiber or part twines Around carbon fiber.When polycarbonate winds carbon fiber, the bonding strength between polycarbonate component and carbon fiber be can be improved.Such as Fruit polycarbonate component is not completely wound around carbon fiber, then there may be the electrophilics that more can be used for being crosslinked in polycarbonate component Side group.

The machinery that can be improved by modifying carbon fibers component surface between polycarbonate component and component carbon fibers connects It connects.For example, the surface roughness of component carbon fibers can be improved.With the increase of surface roughness, polycarbonate component and carbon Connection between fibre fractionation can increase.

The connection of the interface of polycarbonate component and carbon fiber can also be the combination of any of above connection.Namely It says, interface may include covalent bond, ionic bond, Van der Waals force, hydrogen bond, mechanical connection or their any combination.

In some instances, composition may include the second polycarbonate component.Similar to the first polycarbonate component, Di-polycarbonate component may include the repetitive unit that different amounts contains electrophilic side chain.In some instances, the second poly- carbon Acid esters component can be free of electrophilic side chain.Nevertheless, the second polycarbonate component still can be previously described to be similar to The mode of polycarbonate component is connected to carbon fiber.Furthermore it is possible in the second polycarbonate component and the first polycarbonate component Between form interface.In this case, carbon fiber can be pre-coated with the first polycarbonate component.It is then possible to be attached to Second polycarbonate component, to form interface between polycarbonate component and the second polycarbonate component.Interface can wrap Containing covalent bond, ionic bond, Van der Waals force, hydrogen bond, mechanical connection or their any combination.

The intensity of the evaluating combined material of various ways can be passed through.As described in present example, polycarbonate The integrality at the interface between component and carbon fiber can be a kind of mode of evaluation intensity.Integrality can be evaluated by SEM. For example, the space between fiber and polycarbonate component can be related with interface integrity.That is, polycarbonate component and There is no gaps to show stronger connection and on the whole stronger material between carbon fiber.In addition, small between matrix and carbon fiber The presence of fiber can be the instruction of good adherency and integrality.The length of carbon fiber can be measured.Protrude from break surface Staple fiber length be usually good adherency instruction.In addition, host material remaining on carbon fiber is also that adhesiveness changes Kind instruction.In some instances, material has the tensile strength scope greater than one-component.For example, the tensile strength of material Can the tensile strength of polycarbonate component about 100% to component carbon fibers tensile strength about 100% or more In range.

Carbon fiber (carbon fiber) or carbon fiber (carbon fibre) (alternatively, CF, graphite fibre or graphite Fiber) it can be the fiber with any suitable length, diameter and draw ratio.In some instances, fiber can be diameter about 5 The fiber to about 10 microns and being mainly made of carbon atom.The atomic structure of carbon fiber is generally similar to graphite, it includes with The carbon atom piece (graphene film) of regular hexagonal pattern arrangement, difference are the chain mode of these pieces.

Depending on preparing the precursor of fiber, carbon fiber can be random layer (turbostatic) or graphite, or has and deposit In the mixed structure of graphite and both random layer parts.In turbostratic carbon fiber, the irregular folding of carbon atom piece or " wrinkle " exist Together.For example, be random layer derived from the carbon fiber of polyacrylonitrile (PAN), and more than 2200 DEG C at a temperature of be heat-treated it Afterwards, the carbon fiber derived from mesophase pitch is graphite.Turbostratic carbon fiber tends to high tensile, and be heat-treated There is carbon fiber from mesophase pitch high Young's modulus (high rigidity or high stretching tolerance i.e. under a load) and height to lead Heating rate.

The form (for example, random layer is relative to graphite) for not considering carbon fiber, can modify various compositions described herein Component carbon fibers with the surface comprising activation.It can be for example, by electrochemical treatments, corona treatment or ozone treatment Activate the group on the surface of activation.In some embodiments, the surface of activation includes nucleophilic group, so that component carbon fibers Surface includes at least one, but usually a variety of nucleophilic groups that interface can be formed with polycarbonate component interaction. Nucleophilic group can be selected from the group of hydroxyl group, carboxylic group, amino group and their combination.In various examples, activation Surface include about 0.05 atomic concentration % to about 20 atomic concentration % nucleophilic group, or about 0.05 atomic concentration % is to about The nucleophilic group of 8 atomic concentration %.The surface for the activation that method as known in the art determines on component carbon fibers can be used Atomic concentration %.For example, can determine atomic concentration % by x-ray photoelectron spectroscopy (XPS).Typically XPS spectrum is Figure of the number (Y-axis, ordinate) of the electronics detected relative to the combination energy (X-axis, abscissa) of the electronics detected.Each Element can produce the group at the peak feature XPS at value in feature combination, directly authenticated and be present in analyzed material or its table Every kind of element on face.These feature spectral peaks correspond to the electronic configuration of intratomic electronics, for example, 1s, 2s, 2p, 3s etc..Each Number of electrons detected is directly related with the amount of XPS sampling volume interior element in characteristic peak.In order to generate atomic concentration % value, Believed by the way that its signal strength (number of electrons detected) is corrected each original XPS divided by relative sensitivity coefficient (RSF) Number, and relative to all element normalization detected.Due to not detecting hydrogen, these atomic percents do not include hydrogen.

The component carbon fibers of composition may include one or more carbon fibers.That is, component carbon fibers can wrap Containing a variety of carbon fibers, it includes the identical nucleophilic groups for accounting for identical mol%.In some instances, component carbon fibers may include The mixture of the carbon fiber of different nucleophilic groups with the surface for forming different activation.In some instances, different carbon fibers On nucleophilic group can be identical, but the mol% of nucleophilic group can be different.In addition, some carbon fibers can be with Comprising nucleophilic group, and other carbon fibers are free of nucleophilic group, but have other feature to help to be formed interface (for example, thick Rough surface).

The polycarbonate component of composition can be Copolycarbonate.Copolycarbonate includes to be derived from bis-phenol The repetitive unit of derivative and repetitive unit comprising electrophilic side chain.Each repetitive unit can independently be random, block Or alternate configurations.In some specific examples of polycarbonate component, repetitive unit is random configuration.

In various embodiments, Copolycarbonate includes electrophilic side chain along the main chain of copolymer.In some realities It applies in mode, electrophilic side chain can be reacted with the surface of the activation of carbon fiber.Electrophilic side chain may include can with for example It include the electrophilic subdivision of the nucleophilic group reaction on the surface of the activation of component carbon fibers.Present on electrophilic side chain Suitable electrophilic subdivision includes but is not limited to carbonyl group, cyano group, isocyanate group, halogenated alkyl and alkenyl. Suitable carbonyl group includes ester, carboxylic acid and combinations thereof.

Repetitive unit comprising electrophilic side chain has the structure of Formulas I:

R¹It is the aryl group comprising electrophilic side chain.Aryl group can be among copolymer chain, adjacent or contraposition Substituted phenyl group, as shown in following formula II:

Each group R²It can be independently selected from:

At least one R²It can be ester and R³It can be (C₁-C₁₀) alkyl.

In some instances, the repetitive unit comprising electrophilic side chain has structure shown in formula III:

In formula III, phenyl can be what o-, m- or p- position replaced, and R³It can be (C₁-C₂₀) alkyl or (C₁- C₂₀) naphthenic base.In some instances, R³Free methyl, ethyl, propyl, isopropyl, isobutyl group, normal-butyl, Zhong Ding can be selected The group of base, tert-butyl and their combination composition.In some instances, the repetitive unit comprising electrophilic side chain has in formula IV Structure, which show meta position substitutions:

In some instances, the repetitive unit comprising electrophilic side chain can be the end group in Formula V:

As shown, Formula V shows the example of the repetitive unit comprising electrophilic side chain, and wherein the end of repetitive unit is Hydroxyl group.

Polycarbonate component may include polymer or copolymer with repetitive structure carbonate unit shown in Formula IV

Wherein R⁴At least the 60% of the sum of group is aromatic or each R⁴Contain at least one C_6-10Aryl base Group.Each R⁴Group can be identical or different.For example, each R⁴It can be derived from dihydroxy compounds, such as the virtue of Formula VII Bis-phenol represented by fragrant race's dihydroxy compounds or Formula VIII.

In Formula VII, each R^hCarbonyl group, cyano group, isocyanate groups, alkenyl, halogen can independently be Group, for example, bromine, C_1-10Group, such as C_1-10The C that alkyl, halogen replace_1-10Alkyl, C_6-10The C that aryl or halogen replace_6-10 Aryl, and n can be 0 to 4.Suitable carbonyl group includes ester, carboxylic acid and combinations thereof.

In Formula VIII, R^aAnd R^bIt is each independently halogen, C_1-12Alkoxy or C_1-12Alkyl；And p and q are respectively Independently 0 to 4 integer, allow when p or q is less than 4, the chemical valence of each carbon of ring is filled by hydrogen.At one In embodiment, p and q can be individually 0 or p and q is individually 1, and R^aAnd R^bIndividually C_1-3Alkyl group, such as methyl, It is arranged in the meta position of the hydroxyl group in each arylene group.X³It is the bridging for connecting the aromatic group that two hydroxyls replace Base, wherein bridging group and each C₆The hydroxyl substituent of arlydene is in C₆On arlydene each other in ortho position, or contraposition it is (specific Ground, contraposition), such as singly-bound ,-O- ,-S- ,-S (O)-,-S (O)₂,-C (O)-or C_1-18Alkyl group can be cyclic annular or non- Cricoid, aromatic series or non-aromatic, and can also include hetero atom, such as halogen, oxygen, nitrogen, sulphur, silicon or phosphorus.For example, X^a It can be substituted or unsubstituted C_3-18Cycloalkenyl；Formula-C (R^c)(R^d)-C_1-25Alkylidene radical, wherein R^cAnd R^dSeparately For hydrogen, C_1-12Alkyl, C_1-12Naphthenic base, C_7-12Aryl alkyl, C_1-12Miscellaneous alkyl or ring-type C_7-12Heteroarylalkyl；Or formula-C (= R^e)-group, wherein R^eIt is divalent C_1-12Hydrocarbyl group.

In some instances, polycarbonate contains carbonate unit (1) and non-carbonate unit, for example, ester units, poly- silicon Oxygen alkane unit, such as dimethione unit or includes at least one of above-mentioned combination.In some embodiments, ester Unit can be aromatic ester units (for example, resorcinol terephthalate or isophthalic acid ester) or aromatic series-rouge Fat race ester.

In some instances, polycarbonate, which can be, contains bisphenol-A carbon available commercially from SABIC at trade name LEXAN The straight chain homopolymer (BPA-PC) of acid esters unit；Or contain 3mol% available commercially from SABIC at trade name LEXAN CFR 1,1,1- tri- (4- hydroxy phenyl) ethane (THPE) branching agent by interfacial polymerization branch produced, cyanophenol envelope The bisphenol A homopolycarbonate at end.Specific Copolycarbonate includes bisphenol-A and big bisphenol carbonate unit, that is, is derived from and contains At least 12 carbon atoms, for example, the unit of the bis-phenol of 12 to 60 carbon atoms or 20 to 40 carbon atoms.These Copolycarbonates Example include comprising bis- (4- hydroxy phenyl) the phthalimidine carbonate units of bisphenol a carbonate unit and 2- phenyl -3,3'- Copolycarbonate (BPA-PPPBP copolymer, available commercially from SABIC at trade name XHT), include bisphenol a carbonate unit With copolymer (the BPA-DMBPC copolymer, in trade name of bis- (4- hydroxy-3-methyl phenyl) the hexamethylene carbonate units of 1,1- Available commercially from SABIC under DMC) and include bis- (4- hydroxy-3-methyl the phenyl) -3,3,5- of bisphenol a carbonate unit and 1,1- The copolymer (for example, Bayer is come from trade name APEC) of trimethyl-cyclohexane isophorone bisphenol carbonate unit.

The other specific polycarbonate that can be used include right comprising bisphenol a carbonate unit and isophthalic acid ester- Phthalic acid ester-bisphenol-A ester units are poly- (aromatic ester-carbonic ester), depending on the relative ratios of carbonate unit and ester units, Commonly referred to as poly- (carbonate-ester) (PCE) or poly- (phthalic acid ester-carbonic ester) (PPC).Another specific poly- (ester-carbon Acid esters) comprising two acid adding ester of resorcinol isophthalic and terephthalate units and bisphenol a carbonate unit, such as in trade name Available commercially from those of SABIC under LEXAN SLX.

In some instances, polycarbonate can be the poly- (carbonic acid comprising bisphenol a carbonate unit and siloxane unit Ester-siloxanes) copolymer, for example, the block comprising 5 to 200 dimethyl siloxane units, it can quotient such as at trade name EXL Purchased from those of SABIC.The other polycarbonate that can be used include comprising bisphenol a carbonate unit, isophthalic acid methyl esters-right Poly- (ester-siloxanes-carbonic ester) of phthalic acid ester-bisphenol-A ester units and siloxane unit, such as include 5 to 200 diformazans The block of siloxane units, such as available commercially from those of SABIC at trade name FST.

Poly- (aliphatic ester-carbonic ester) can be used, such as comprising bisphenol a carbonate unit and decanedioic acid-bisphenol-A ester units Those of, such as available commercially from those of SABIC at trade name LEXAN HFD.

The combination that polycarbonate Yu other polymer can be used, it is, for example, possible to use bisphenol-a polycarbonates and ester, such as The combination of poly- (mutual-phenenyl two acid bromide two alcohol ester) or poly- (ethylene glycol terephthalate), each of which can be half Crystallization is unbodied.These combinations are at trade name XENOY and XYLEX available commercially from SABIC.

Double phenol polycarbonate repetitive unit can be derived from a variety of different bis-phenols.Suitable bis-phenol includes selected from the following Group those of bis- (4- hydroxy phenyl) methane of 1,1-, bis- (4- hydroxy phenyl) ethane of 1,1-, bis- (4- hydroxy phenyl) butane of 2,2-, Bis- (4- hydroxy phenyl) octanes of 2,2-, bis- (4- hydroxy phenyl) propane of 1,1-, 1,1- bis- (4- hydroxy phenyl)-normal butanes, 2,2- Bis- (4- hydroxyl -1- aminomethyl phenyl) propane, 4,4 '-dihydroxybiphenyls, bis- (4- hydroxy phenyl) methane, bis- (4- hydroxy phenyls) two Bis- (4- hydroxy phenyl) ethane of phenylmethane, 1,2-, bis- (4- the hydroxy phenyl) -1- diphenylphosphino ethanes of 1,1-, 2- (4- hydroxy phenyl) - 2- (3- hydroxy phenyl) propane, bis- (4- hydroxy phenyl) phenylmethanes, bis- (hydroxy phenyl) pentamethylene of 1,1-, bis- (the 4- hydroxyls of 1,1- Base phenyl) hexamethylene, bis- (4- hydroxy phenyl) isobutenes of 1,1-, bis- (4- hydroxy phenyl) cyclododecanes of 1,1-, trans- -2,3- pairs Bis- (4- hydroxy phenyl) adamantane of (4- hydroxy phenyl) -2- butylene, 2,2-, (bis- (4- hydroxy phenyl) toluene of α, α ' -, bis- (4- hydroxyls Base phenyl) acetonitrile, bis- (4- hydroxy phenyl) ethylene of the chloro- 2,2- of 1,1- bis-, bis- (4- hydroxy phenyl) ethylene of the bromo- 2,2- of 1,1- bis-, Bis- (4- the hydroxy phenyl) -2- butanone of 3,3-, bis- (4- the hydroxy phenyl) -1,6- acetyl butyryls of 1,6-, ethylene glycol are bis- (4- hydroxy phenyl) Ether, bis- (4- hydroxy phenyl) ethers, bis- (4- hydroxy phenyl) thioethers, bis- (4- hydroxy phenyl) sulfoxides, bis- (4- hydroxy phenyl) sulfones, 9, Bis- (4- hydroxy phenyl) fluorenes of 9-, 2- phenyl -3,3- pairs-(4- hydroxy phenyl) phthalimide (PPPBP), the bis- (4- of 2,2- Hydroxyl -3- bromophenyl) propane, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, bis- (the 3- ethyl -4- hydroxy phenyls) third of 2,2- Bis- (3- n-propyl -4- hydroxy phenyl) propane of alkane, 2,2-, 2,2- bis- (3- isopropyl -4- hydroxy phenyl) propane, the bis- (3- of 2,2- Sec-butyl -4- hydroxy phenyl) propane, bis- (3- tert-butyl-hydroxy phenyl) propane of 2,2-, the bis- (3- cyclohexyl -4- hydroxyls of 2,2- Phenyl) propane, bis- (3- allyl -4- hydroxy phenyl) propane of 2,2-, 2,2- bis- (3- methoxyl group -4- hydroxy phenyl) propane, 2, Bis- (4- hydroxy phenyl) hexafluoropropane of 2-, the chloro- 2,2- of 1,1- bis- bis- (5- phenoxy group -4- hydroxy phenyl) ethylene, double-(4- hydroxyl Phenyl) diphenyl methane), bis- (4- hydroxy diphenyl) methane, 2,2- bis- (4- hydroxyl -3- isopropyl-phenyl) propane, 5,5 ' - (1- methyl ethidine)-bis- [1,1 '-(diphenyl) -2- alcohol] propane, bis- (4- the hydroxy phenyl) -3,3,5- trimethyl-rings of 1,1- Bis- (4- the hydroxy phenyl)-hexamethylenes of hexane, 1,1-, bis- (4- hydroxy phenyl) phthalimides of 2- phenyl -3,3'- and they Combination.In specific example, repetitive unit derived from bis-phenol can be bisphenol-A (2,2- bis- (4- hydroxy phenyl) propane).Appoint What these repetitive unit may be embodied in polycarbonate component.Because there are a variety of different types of poly- carbonic acid that can be used Ester units and unit containing electrophilic side group may exist very big difference in the polycarbonate component that can be formed.Below Show a kind of this example, wherein polycarbonate repeat unit is monomer derived from bisphenol-A, and contains electrophilic side group Repetitive unit is derived from ethyl -3,5- dihydroxy-benzoic acid ester.This poly- carbonic acid is shown in the structure in following formula IX and X Ester component:

Difference between Formula IX and Formula X is that Formula X is shown and is formed by the monofunctional hydroxyl monomer comprising electrophilic side chain Repetitive unit.Depending on the desired property of composition, the amount of each repetitive unit can change in polycarbonate.For example, such as Fruit it is expected more covalent bonds in interface, and can increase can be from poly- carbonic acid made of the repetitive unit containing electrophilic side group The amount of ester.However, at least 50mol% of the typically polycarbonate component of repetitive unit derived from bis-phenol.For example, bis-phenol spreads out Raw repetitive unit can be in the range of the about 50mol% to about 99mol% of Copolycarbonate or polycarbonate is total In the range of the about 70mol% to about 99mol% of polymers.

On the contrary, the typically Copolycarbonate of the repetitive unit containing electrophilic side group is less than 50mol%. For example, the repetitive unit of the side group containing electrophilic can be in the range of the about 0.2mol% to about 50mol% of Copolycarbonate In the range of the about 0.2mol% to about 20mol% of interior perhaps Copolycarbonate or the pact of Copolycarbonate In the range of 0.2mol% to about 9mol%.In some instances, electrophilic side group repetitive unit can only be used as end group It is present on Copolycarbonate.

As described above, the presence of the repetitive unit of the side chain containing electrophilic allows the electrophilic side chain in polycarbonate component Reaction between carbonate functional.Reaction between electrophilic side chain and carbonate functionalities causes to generate between them Key.Therefore, there may be crosslinkings between polymer chain.The definite degree of electrophilic side chain crosslinking can be different.For example, about The repetitive unit comprising electrophilic side chain of 0mol% to about 100mol% can be crosslinked.It is in some instances about 5% to about 95%, or about 30% to about 95%, or about 60% to about 95%, or about 70% to about 95%.The intensity of polycarbonate component with Crosslinking the side group containing electrophilic repetitive unit mol% increase and increase.However, with the raising of mol%, poly- carbonic acid Ester component and the ability of carbon fiber covalent bonding may be decreased.In the parent comprising crosslinking that wherein may exist relatively high mol% In the example of the repetitive unit of electronics side chain, the interface between polycarbonate component and carbon fiber can pass through Van der Waals force, hydrogen Key is formed in various degree by mechanical connection.The nucleophilic group of uncrosslinked electrophilic side chain and component carbon fibers is arbitrarily anti- It answers.

Crosslinking between the repetitive unit of the side chain containing electrophilic can be intermolecular cross-linking, intramolecular crosslinking or their group It closes.The flame-retarding characteristic of material can be improved in the presence of crosslinking.That is, the flame-retarding characteristic of material increases with the raising of the degree of cross linking Add.The flame-retarding characteristic of material can also be improved by the material including flame-retardant additive.In the composite, fire-retardant addition Agent can be relative to polycarbonate component total weight in the about 0.4wt% to about 20wt% of material, or about 4wt% is to about In the range of 15wt%.Some illustrative examples of fire retardant include such as organic phosphorus compound, such as organophosphorus ester (salt) (packet Include trialkylphosphate, such as triethyl phosphate, three (2- chloropropyl) phosphates and triaryl phosphate, such as triphenyl phosphate and Diphenyl phosphate cresols ester, resorcinol be double-diphenyl phosphoester, resorcinol diphosphate and phosphoric acid aromatic ester), phosphite ester (salt) (including trialkyl phosphite, triarylphosphite and mixed alkyl-aryl-group phosphite ester), phosphonate ester (salt) (including diethyl ethylphosphate, dimethyl methyl phosphonate), polyphosphate (salt) (including melamine phosphate, ammonium polyphosphate), Poly- phosphite ester (salt), polyphosphonates (salt), phosphinate (salt) (including three (diethyl phosphonous acid aluminium))；Halogenated fire-retardants, Such as chlorendic acid derivative and chlorinated paraffin；Organic bromide, such as deca-BDE (decaBDE), decabromodiphenylethane, polymerization Brominated compound, such as brominated Polystyrene, bromination carbonate oligomer (BCO), brominated epoxide oligomer (BEO), four Phthalate bromine acid anhydride, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD)；Metal hydroxides, as magnesium hydroxide, The hydrate of aluminium hydroxide, cobalt hydroxide and above-mentioned metal hydroxides；And their combination.Fire retardant can be response type resistance Combustion property is (including the polyalcohol containing phosphorus group, 10- (2,5- dihydroxy phenyl) -10H-9- oxa- -10- phospha-phenanthrene -10- oxidation Object, lactone modified polyester, ethylene glycol containing phosphorus bis- (diphenyl phosphates), neopentyl glycol bis- (diphenyl phosphates), amine and hydroxyl The functionalized siloxane oligomer of base).These fire retardants can be used in combination individually or with other fire retardants.

Composite material as described above can be formed in a number of different ways.For example, compression molded or note can be passed through It penetrates method of moulding and forms composite material.May include using the example that compression molded method forms the suitable method of composite material The composition of polycarbonate component and carbon fiber is placed in mold.It, then can be by mold once composition is in mold It heats and mold can be applied pressure to form composite material.

In some instances, can before being added polycarbonate component or carbon fiber to mold heating mould.At it In its example, polycarbonate component and carbon fiber is added in different time.For example, mould can be added polycarbonate component first Have and melts.Once mold can be added in carbon fiber by polycarbonate melt.

Composition can be made to solidify during heating process.The temperature of heating mould can change, but usually can be high In the T of polycarbonate component_g.Suitable temperature range for heating mould can be about 100 DEG C to about 350 DEG C, Huo Zheyue 200 DEG C to about 350 DEG C.

Mold can be heated about 1 minute to about 60 minutes, perhaps about 1 minute to about 30 minutes or about 5 minutes to about 30 minutes.In heating mould, mold can also be made to be subjected to the pressure applied.Pressure can at about 0.5 ton to about 4 tons, or In the range of about 1 ton to about 2 tons.

Embodiment

By reference to the following example provided by way of illustration, multiple embodiment party of the invention may be better understood Formula.The present invention is not limited to embodiment provided herein.In embodiment, the Copolycarbonate containing electrophilic side group (ESG) It can be by the repetitive unit derived from bisphenol-A and as formed above for the ethyl -3,5- dihydroxy-benzoic acid ester described in Formula IX. In embodiment, PC105 is free from the Linear polycarbonate homopolymer of electrophilic side group.

In embodiment, SEM refers to scanning electron microscope, and GPC refers to that gel permeation chromatography, ATR-FTIR refer to decaying It is totally reflected Fourier transform infrared spectroscopy.

Comparative example 1:PC105 is heated 1 minute at 200 DEG C

It is (1 hour dry in vacuum drying oven at 100 DEG C using about 300mg PC105 particle；M_w=59,400g/ rubs You；PD=2.5 it) is prepared directly using following steps by compression molded with the uncoated carbon fiber bundle (24K) of certain length The film of 250 μ m-thicks of diameter 30mm: (1) heating mold 1 minute at 200 DEG C so that polymer melting and (2) use 2 tons of pressures In addition power heats 1 minute at 200 DEG C to prepare film.After step (1) and (2), gpc analysis (PS data) shows PC base Matter has M_w=59,200 and PD=2.5.It is limited that this shows that the combination of temperature and time has the molecular weight distribution of PC105 It influences.

It is stayed overnight handling compression molded film with 20ml methylene chloride (DCM), residual fiber is then cleaned into (2 × 20ml) And be dried in vacuo after (80 DEG C overnight), the ATR-FTIR imaging of fiber surface (draws 1800 and 1710cm^-1Between the peak C=O The IR image of area) PC of the display on the fiber surface without remnants.

The SEM image for the composite material that Fig. 1 is shown.Fig. 2 is the enlarged drawing of composite material shown in FIG. 1.For Sample preparation using the sem analysis of freezing crack and the cross section of sputtering coating (5nm PtPD) show matrix and fiber it Between long fibre and wide arc gap, the two is all typical for the poor adhesion between fiber and matrix.According to SEM and ATR- FTIR analysis, it can be deduced that conclusion, there are undesirable combinations between PC105 matrix and uncoated carbon fiber.

Comparative example 2:PC105 is heated 1 minute at 300 DEG C

Using about 300mg PC105 particle (at 100 DEG C dry 1 hour in vacuum drying oven；M_w=59,400g/ rubs You；PD=2.5 it) is prepared directly using following steps by compression molded with the uncoated carbon fiber bundle (24K) of certain length The film of 250 μ m-thicks of diameter 30mm: (1) heating mold 1 minute at 300 DEG C so that polymer melting and (2) use 2 tons of pressure Heat 1 minute in addition at 300 DEG C to prepare film.(5nm PtPD) is coated using freezing crack and sputtering for sample preparation The sem analysis of cross section shows the wide arc gap between long fibre and matrix and fiber, and the two is between fiber and matrix Poor adhesion be all typical.After step (1) and (2), gpc analysis (PS data) shows that PC matrix has M_w=58, 800 and PD=2.5.This shows that the combination of temperature and time has limited influence to the molecular weight distribution of PC105.

Although higher temperature, which is used for compression molded, reduced resin viscosity, does not improve fibre compared with comparative example 1 The wetting of dimension and interface adhesiveness.

Comparative example 3:PC105 is heated 10 minutes at 300 DEG C

Using about 300mg PC105 particle (at 100 DEG C dry 1 hour in vacuum drying oven；M_w=59,400g/ rubs You；PD=2.5 it) is prepared directly using following steps by compression molded with the uncoated carbon fiber bundle (24K) of certain length The film of 250 μ m-thicks of diameter 30mm: (1) heating mold 10 minutes at 300 DEG C so that polymer melting and (2) use 2 tons of pressures In addition power heats 10 minutes at 300 DEG C to prepare film.After step (1) and (2), gpc analysis (PS data) shows PC base Matter has M_w=56,800 and PD=2.5.It is limited that this shows that the combination of temperature and time has the molecular weight distribution of PC105 It influences.

Length is shown using the sem analysis of freezing crack and the cross section of sputtering coating (5nm PtPD) for sample preparation Both with staple fiber.Compared with comparative example 1 and 2, the gap between fiber and matrix also seems smaller, and according to fiber surface Small fiber between the PC and fiber and matrix of upper remnants, PC are preferably adhered to fiber surface.When will be melted at 300 DEG C Between from 1 minute (comparative example 2) improve resulted in 10 minutes slightly improve fiber wetting and interface adhesiveness.

Comparative example 4:PC105 is heated 30 minutes at 325 DEG C

Using about 300mg PC105 particle (at 100 DEG C dry 1 hour in vacuum drying oven；M_w=59,400g/ rubs You；PD=2.5 it) is prepared directly using following steps by compression molded with the uncoated carbon fiber bundle (24K) of certain length The film of 250 μ m-thicks of diameter 30mm: (1) heating mold 30 minutes at 325 DEG C so that polymer melting and (2) use 2 tons of pressures 1 minute is heated under power in addition at 325 DEG C to prepare film.After step (1) and (2), gpc analysis (PS data) shows PC base Matter has M_w=55,600 and PD=2.5.It is limited that this shows that the combination of temperature and time has the molecular weight distribution of PC105 It influences.

It may be concluded that even if when using the combination of high temperature (325 DEG C) and curing time (30 minutes), in PC105 It is not present between the fiber surface of uncoated carbon fiber or there is only weak non-covalent linking.

The thermal desorption GC-TOFMS of comparative example 5:PC105

About 8mg PC105 particle (2 hours dry in vacuum drying oven at 120 DEG C) thermal desorption 10 minutes at 300 DEG C After 30 minutes, volatile matter is analyzed using GC-TOFMS.It analyzes total ion chromatography (TIC) and relevant peak is quantified, such as Shown in table 1.

Table 1:GC-TOFMS result

Comparative example 6: it single fiber pull-out Lexan HF-1110: is heated 30 seconds at 300 DEG C

Single fiber is carried out in Leibniz-Institut f ü r Polymerforschung Dresden e.V. (IPF) to pull out It tests out, to embedded fiber and extracts equipment manufactured by both tests use research.Using following sequence, by 300 DEG C Under 150 μm of uncoated single carbon fibers are embedded in Lexan HF-1110 (at 120 DEG C dry 2 hours) under an argon In and generate single fiber model composite.Polymer is heated to 300 DEG C with the speed of 15 DEG C/min, and is protected at 300 DEG C It holds 30 seconds.150 μm of fibers are embedded, and matrix is kept for 30 seconds at 300 DEG C.Then, matrix was cooled to room in 30 minutes Temperature.Table 2 is shown to be measured based on 15-20 times, makes single fiber that required function (W is detached from and extracted from matrix_Always)。

Table 2: make the function of fiber degumming and extraction from matrix

Embodiment 1:8.6mol% ester side group (ESG) Copolycarbonate: solidify 1 minute at 200 DEG C

Using about 300mg 8.6mol%ESG Copolycarbonate powder (at 100 DEG C in vacuum drying oven it is dry 1 small When) and one section of unsized carbon fiber bundle (24K) using following steps pass through compression molded 250 μ m-thicks for preparing diameter 30mm Film: (1) mold is heated 1 minute at 200 DEG C so that polymer melting and (2) using 2 tons of pressure at 200 DEG C in addition plus Heat 1 minute to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(52,436g/mol) is similar with PD (2.76) In starting powder (M_w=49,585g/mol；PD=2.80), limited amount crosslinking/chain lengthening has occurred.

Length is shown using the sem analysis of freezing crack and the cross section of sputtering coating (5nm PtPD) for sample preparation Wide arc gap between fiber and matrix and fiber, the two are all typical for the poor adhesion between fiber and matrix.

It may be concluded that the comparative example 1 that PC105 is wherein used as to matrix is similar to, in uncoated carbon fiber and not There are undesirable combinations between cured 8.6mol%ESG Copolycarbonate.

Embodiment 2:8.6mol%ESG Copolycarbonate: solidify 10 minutes at 200 DEG C

It uses about 300mg 8.6mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 10 minutes at 200 DEG C so that polymer melting and (2) are another at 200 DEG C using 2 tons of pressure External heat 1 minute to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(52,115g/mol) is similar with PD (2.75) In starting powder (M_w=49,585g/mol；PD=2.80), therefore limited amount crosslinking/chain lengthening has occurred.

Curing time was increased to the wetting for not improving fiber for 10 minutes from 1 minute (embodiment 1) at 200 DEG C and interface is glued It is attached.

Embodiment 3:8.6mol%ESG Copolycarbonate: solidify 10 minutes at 250 DEG C

It uses about 300mg 8.6mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 10 minutes at 250 DEG C so that polymer melting and (2) are another at 250 DEG C using 2 tons of pressure External heat 1 minute to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(51,951g/mol) is similar with PD (2.73) In starting powder (M_w=49,585g/mol；PD=2.80), therefore limited amount crosslinking/chain lengthening has occurred.

Length is shown using the sem analysis of freezing crack and the cross section of sputtering coating (5nm PtPD) for sample preparation And staple fiber.In addition, compared with Example 2, the remaining PC on fiber surface is the improved instruction of adherency.Fig. 3 shows to obtain Composite material SEM image.Fig. 4 is the amplification picture of composite material shown in Fig. 3.

Stayed overnight handling compression molded film with 20ml methylene chloride (DCM), then by remaining fiber cleaning (2 × It 20ml) and is dried in vacuo after (80 DEG C overnight), the ATR-FTIR imaging of fiber surface (draws 1800 and 1710cm^-1Between C The IR image of=O peak area) show remaining PC on fiber surface.

It is observed between matrix and fiber surface when solidifying 10 minutes at 250 DEG C when instead of 200 DEG C (embodiment 2) Improved combination, this makes it more difficult to completely remove PC from fiber surface.

Embodiment 4:8.6mol%ESG Copolycarbonate: solidify 10 minutes at 300 DEG C

It uses about 300mg 8.6mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 10 minutes at 300 DEG C so that polymer melting and (2) use under 2 tons of pressure at 300 DEG C In addition 1 minute is heated to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(53,552g/mol) is similar with PD (2.61) In starting powder (M_w=49,585g/mol；PD=2.80), therefore limited amount crosslinking/chain lengthening has occurred.

The sem analysis for the cross section that sample preparation coats (5nm PtPD) using freezing crack and sputtering is shown short Fiber and the matrix for closely surrounding fiber, the two is the instruction of good adhesion between fiber and matrix.

Stayed overnight handling compression molded film with 20ml methylene chloride (DCM), then by the cleaning of remaining fiber (2 × It 20ml) and is dried in vacuo after (80 DEG C overnight), the ATR-FTIR imaging of fiber surface (draws 1800 and 1710cm^-1Between C The IR image of=O peak area) show remaining PC on fiber surface.

Solidification temperature is improved from 250 DEG C (embodiment 3) to 300 DEG C and is further improved between matrix and fiber surface In conjunction with this makes it difficult to completely remove fiber from PC matrix.This improved combination can be attributed to ester functional group, because Under the same terms, the slight improvement (comparative example 3) of interface adhesiveness and fiber wetting only observed for PC105.

Embodiment 5:8.6mol%ESG Copolycarbonate: solidify 10 minutes at 325 DEG C

It uses about 300mg 8.6mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 10 minutes at 325 DEG C so that polymer melting and (2) are another at 325 DEG C using 2 tons of pressure External heat 1 minute to prepare film.By the gpc analysis (PS data) of matrix it may be concluded that due to M_wIncrease to 56,813g/ Mol (starting powder M_w=49,585g/mol), a large amount of crosslinking/chain lengthening has occurred, this also results in higher 3.00 PD (starting powder PD=2.80).It is stayed overnight handling compression molded film with 20ml methylene chloride (DCM), then by remaining fiber Cleaning (2 × 20ml) is simultaneously dried in vacuo after (80 DEG C overnight), and the ATR-FTIR imaging of fiber surface (draws 1800 Hes 1710cm^-1Between C=O peak area IR image) show remaining PC on fiber surface.Obviously, in matrix and fiber table Improved combination is produced between face, this, which makes it difficult to clean by DCM, completely removes fiber from the surface PC.

ATR-FTIR result is similar to embodiment 3 and 4, and wherein ESG Copolycarbonate is solid at 250 DEG C and 300 DEG C respectively Change 10 minutes.It is using 325 DEG C of latent defect since more effective crosslinking/chain lengthening, possibility discharge more at such a temperature More ethylene and CO₂, this causes the amount of bubble to increase.

Embodiment 6:8.6mol%ESG Copolycarbonate: solidify 1 minute at 325 DEG C

It uses about 300mg 8.6mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 1 minute at 325 DEG C so that polymer melting and (2) are another at 325 DEG C using 2 tons of pressure External heat 1 minute to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(52,513g/mol) is similar with PD (2.75) In starting powder (M_w=49,585g/mol；PD=2.80), limited amount crosslinking/chain lengthening has occurred.

Length is shown using the sem analysis of freezing crack and the cross section of sputtering coating (5nm PtPD) for sample preparation With short fiber, wherein between fiber and matrix only have small―gap suture.In addition, PC and fiber remaining on fiber surface and matrix Between small fiber presence be adhesiveness improve instruction.

Stayed overnight handling compression molded film with 20ml methylene chloride (DCM), then by the cleaning of remaining fiber (2 × It 20ml) and is dried in vacuo after (80 DEG C overnight), the ATR-FTIR imaging of fiber surface (draws 1800 and 1710cm^-1Between C The IR image of=O peak area) PC of the display on the fiber surface without remnants.

Compared with embodiment 1 (at 200 DEG C 1 minute), which shows significant preferably fiber wetting and Interface Adhesion Property, but it is not so good as embodiment 4 (at 300 DEG C 10 minutes), wherein PC passes through more tightly around fiber and after DCM cleaning PC of the ATR-FTIR image checking of fiber surface to remnants.Obviously, fiber wetting and interface adhesiveness are improved at high temperature, But the result taken more time to realize embodiment 4 (at 300 DEG C 10 minutes).With embodiment 5 (at 325 DEG C 10 minutes) phase Be than the advantage that, curing time shortens since crosslinking/chain lengthening is less effective, form less bubble (ethylene and CO₂)。

Embodiment 7:8.6mol%ESG Copolycarbonate: solidify 5 minutes at 325 DEG C

It uses about 300mg 8.6mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 5 minutes at 325 DEG C so that polymer melting and (2) are another at 325 DEG C using 2 tons of pressure External heat 1 minute to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(53,669g/mol) is similar with PD (2.81) In starting powder (M_w=49,585g/mol；PD=2.80), therefore limited amount crosslinking/chain lengthening has occurred.

Obviously, need to reach more than 5 minutes at 325 DEG C embodiment 4 and 5 as a result, wherein DCM cleaning after, lead to The ATR-FTIR image checking of fiber surface is crossed to PC.

Embodiment 8:8.6mol%ESG Copolycarbonate: solidify 30 minutes at 325 DEG C

It uses about 300mg 8.6mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 30 minutes at 325 DEG C so that polymer melting and (2) use under 2 tons of pressure at 325 DEG C In addition 1 minute is heated to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_wIncrease to 70,967g/mol (starting powder M_w= 49,585g/mol), therefore a large amount of crosslinking/chain lengthening has occurred.However, degradation also results in Mn and is reduced to 14,692g/mol (starting powder Mn=17,716g/mol).These parallel events cause PD to increase to 4.83 from 2.80 (starting powders).

Since film quality is bad, (bubble is more, frangible, brown and is difficult to from the aluminium foil for being used for protective film during compression moulding Remove), it is therefore desirable to the film of SEM research can be used to generate for following additional step: (1) from by method system as described above Fibre bundle and (2) are removed in standby compression molded film by these " coating " fibers and about 300mg PC105 particle (100 It is 1 hour dry in vacuum drying oven at DEG C) combination.In order to obtain film by compression molded 250 μ m-thicks for preparing new diameter 30mm, It uses following steps: (1) heating mold 1 minute at 200 DEG C so that polymer melting and (2) use 2 tons of pressure at 200 DEG C Lower in addition heating 1 minute to prepare film.

The sem analysis for the cross section that sample preparation coats (5nm PtPD) using freezing crack and sputtering is shown short Fiber, mesostroma closely surrounds fiber and the fiber on its surface is completely covered in PC matrix.The two is the instruction of good adhesion. Fig. 5 shows the SEM image of gained composite material.Fig. 6 is the picture of the amplification of composite material shown in fig. 5.

In embodiment 6 (325 DEG C, 1 minute), 325 DEG C of high temperature improves fiber wetting and interface adhesiveness, simultaneously 30 minutes in this embodiment long curing times further improved the combination between fiber and matrix.However, since crosslinking/chain is stretched Long reaction forms numerous air-bubble (ethylene and CO₂) and degrade so that film is frangible and make its that brown, therefore the quality of film be presented It is bad.The latter makes these conditions advantageous not as good as embodiment 4, wherein shorter time (10 minutes) and lower temperature (300 DEG C) also result in the improvement combined between fiber and matrix, while film quality also more preferable (less bubble and no discoloration and drop Solution).

Embodiment 9:4.9mol%ESG Copolycarbonate: 1 minute under 200 DEG C of solidifications

It uses about 300mg 4.9mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 1 minute at 200 DEG C so that polymer melting and (2) are another at 200 DEG C using 2 tons of pressure External heat 1 minute to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(51,853g/mol) is similar with PD (2.71) In starting powder (M_w=48,677g/mol；PD=2.76), therefore limited amount crosslinking/chain lengthening has occurred.

It may be concluded that it is similar to PC105 (comparative example 1) and 8.6mol%ESG Copolycarbonate (embodiment 1), There are undesirable combinations between uncoated carbon fiber and uncured 4.9mol%ESG Copolycarbonate.

Embodiment 10:4.9mol%ESG Copolycarbonate: solidify 10 minutes at 200 DEG C

It uses about 300mg 4.9mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 10 minutes at 200 DEG C so that polymer melting and (2) are another at 200 DEG C using 2 tons of pressure External heat 1 minute to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(51,135g/mol) is similar with PD (2.69) In starting powder (M_w=48,677g/mol；PD=2.76), therefore limited amount crosslinking/chain lengthening has occurred.

Curing time was improved from 1 minute (embodiment 9) to 10 minutes to wetting and the interface for not improving fiber at 200 DEG C Adhesiveness.

Embodiment 11:4.9mol%ESG Copolycarbonate: solidify 10 minutes at 250 DEG C

It uses about 300mg 4.9mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 10 minutes at 250 DEG C so that polymer melting and (2) are another at 250 DEG C using 2 tons of pressure External heat 1 minute to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(50,412g/mol) is similar with PD (2.69) In starting powder (M_w=48,677g/mol；PD=2.76), limited amount crosslinking/chain lengthening has occurred.

Length is shown using the sem analysis of freezing crack and the cross section of sputtering coating (5nm PtPD) for sample preparation With short fiber.In addition, compared with Example 10, the remaining PC on fiber surface is the instruction that adhesiveness improves.

When (embodiment 10) solidifies 10 minutes at 250 DEG C rather than at 200 DEG C, in SEM and ATR-FTIR analysis two It observed the improvement combined between matrix and fiber surface in person.

Embodiment 12:4.9mol%ESG Copolycarbonate: solidify 10 minutes at 300 DEG C

It uses about 300mg 4.9mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 10 minutes at 300 DEG C so that polymer melting and (2) are another at 300 DEG C using 2 tons of pressure External heat 1 minute to prepare film.By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(51,307g/mol) and PD (2.72) is similar to starting powder (M_w=48,677g/mol；PD=2.76), limited amount crosslinking/chain lengthening has occurred.

Solidification temperature is improved from 250 DEG C (embodiment 11) to 300 DEG C and is further improved between matrix and fiber surface Combination.This improved combination can be attributed to ester functional group, because under the same conditions, only observed for PC105 The smaller improvement (comparative example 3) of interface adhesiveness and fiber wetting.Similar to 8.6mol%ESG Copolycarbonate (embodiment 4), In 10 minutes at 300 DEG C curing times for improving seemingly good combination for the combination between fiber and matrix.

Embodiment 13:4.9mol%ESG Copolycarbonate: solidify 1 minute at 300 DEG C

It uses about 300mg 4.9mol%ESG Copolycarbonate powder (drying 1 hour in vacuum drying oven at 100 DEG C) Pass through compression molded 250 μ for preparing diameter 30mm using following steps with the uncoated carbon fiber bundle (24K) of certain length The film of m thickness: (1) heating mold 1 minute at 300 DEG C so that polymer melting and (2) are another at 300 DEG C using 2 tons of pressure External heat 1 minute to prepare film.

By the gpc analysis (PS data) of matrix it may be concluded that due to M_w(49,934g/mol) is similar with PD (2.67) In starting powder (M_w=48,677g/mol；PD=2.76), therefore limited amount crosslinking/chain lengthening has occurred.

Although higher temperature, which is used for compression molded, reduced resin viscosity, does not improve fibre compared with comparative example 9 The wetting of dimension and interface adhesiveness.

The thermal desorption GC-TOFMS of 14:4.9 moles of %ESG Copolycarbonate of embodiment

4.9 moles of %ESG Copolycarbonate powder of about 5mg (2 hours dry in vacuum drying oven at 120 DEG C) are 300 At DEG C after thermal desorption 10 minutes and 30 minutes, volatile matter is analyzed by GC-TOFMS.Analyze total ion chromatography (TIC) and to correlation Peak is quantified, as shown in the table 1 in comparative example 5.

Embodiment 15: 4.9 moles of %ESG Copolycarbonates of single fiber pull-out: solidify 30 seconds at 300 DEG C

Using following sequence, by the way that 150 μm of uncoated single carbon fibers are embedded under an argon at 300 DEG C Single fiber model composite is generated in 4.9 moles of %ESG Copolycarbonates (2 hours dry at 120 DEG C).Firstly, will gather Carbonic ester is heated to 300 DEG C with the speed of 7 DEG C/min, and is kept for 30 seconds at 300 DEG C.Embed 150 μm of fibers, and by mixture It is kept for 30 seconds at 300 DEG C.Then, mixture is cooled to room temperature in 30 minutes.To be lower than in comparative example 6 for Lexan (respectively 7 DEG C/min and 15 DEG C/min) progress melting process of speed of HF-1110 are to limit bubble formation.

Table 2 in comparative example 6 is shown to be measured based on 15-20 times, needed for so that single fiber is detached from and is extracted from matrix Function (W_Always).Compared with the test of the single fiber pull-out of Lexan HF-1110, so that fiber is detached from and is extracted from 4.9%ESG PC is needed Want 2 times of function.

Embodiment 16: 4.9 moles of %ESG Copolycarbonates of single fiber pull-out: solidify 10 minutes at 300 DEG C

Using following sequence, by the way that 150 μm of uncoated single carbon fibers are embedded under an argon at 300 DEG C Single fiber model composite is generated in 4.9 moles of %ESG Copolycarbonates (2 hours dry at 120 DEG C).Firstly, will gather Carbonic ester is heated to 300 DEG C with the speed of 7 DEG C/min, and is kept for 30 seconds at 300 DEG C.Embed 150 μm of fibers, and by mixture It is kept for 10 minutes at 300 DEG C.Then, mixture is cooled to room temperature in 30 minutes.

It is used to make polymer melting to limit bubble formation similar to the low heating speed of 15,7 DEG C/min of embodiment.So And after embedded fiber, when polymer to be kept to 10 minutes (relative to 30 seconds in embodiment 15) at 300 DEG C, generate Bubble, this indicates the reaction of ester side group.

Table 2 in comparative example 6 shows function (W required for making single fiber be detached from and extract_Always).The value of the present embodiment only base It is measured in 9 times, because most of fiber is broken during extracting test.In addition, making fiber needed for being detached from and extracting in matrix Function (average value of 9 fibers) be embodiment 15 (wherein fiber embeds only 30 seconds in 4.9 moles of %ESG Copolycarbonates) In 2 times of height.

As proved by embodiment, the overall characteristic of the material of formation depends on many factors.Those factors include Solidification temperature, the mol% of retention time and ESG material.For the embodiment comprising 8.6mol%ESG Copolycarbonate, discovery Best product be make under conditions of 300 DEG C, 10 minutes retention times it is product solidified caused by.It was found that solidification temperature usually needs It is about 300 DEG C of fiber wetting and Interface Adhesions to show improvement.Additionally, it was found that 10 minutes retention times below are usual It not will lead to the product for generating and there is excellent Interface Adhesion.

In general, fiber wetting and interface adhesiveness can be improved in the at a temperature of solidification higher than 300 DEG C.But it if keeps Time is 10 minutes or more, then observes bubble, discoloration and the degradation of product.Additionally, it was found that even if at higher temperatures, Retention time less than 10 minutes, which not will lead to, generates excellent adherency as with those of higher retention time embodiment Property.Similarly, even if being formed by product using the solidification temperature less than 300 DEG C will not when using the longer retention time Generate the product for showing and solidifying the degree of adhesion as those of about 10 minutes at 300 DEG C.

When being subjected to a variety of solidification temperatures and retention time, the product comprising 4.9mol%ESG Copolycarbonate of formation Show similar result.

Although being formed by product in co-polycarbonate component and carbon fiber using 8.6mol% 4.9mol%ESG material The adhesiveness of variation is shown between dimension, but two kinds of products exhibit improvements over the adhesiveness of those of comparative example.Include The comparative example of 0mol%ESG consistently shows wide arc gap between polycarbonate component and carbon fiber.This indicates bad viscous Attached property.

Used terms and expressions are used as Terminology rather than limiting term, and are using these terms and expressions When, it is not intended to any equivalent form of shown and feature or part thereof is excluded, but is to recognize that the range in embodiment of the present invention Interior a variety of change is possible.Thus, it will be appreciated that although being specifically disclosed by specific embodiment and optional feature The present invention, but those skilled in the art can take the modifications and variations of concepts disclosed herein, and these modifications and Variation is considered as in the range of embodiments of the present invention.

Other embodiment.

Following implementation is provided, the number of embodiment is not construed as the expression to level of significance:

Embodiment 1 provides composition, it includes:

Polycarbonate component, it includes the repetitive units containing electrophilic side chain；

Component carbon fibers, it includes the surfaces of activation, wherein the surface activated includes nucleophilic group；With

Interface between polycarbonate component and component carbon fibers.

Embodiment 2 provides the composition of embodiment 1, wherein the surface activated includes nucleophilic group.

Embodiment 3 provides the composition of any one of embodiment 1 or 2, and wherein nucleophilic group, which is selected from, hydroxyl base The group that group, carboxylic group, amino group and their combination form.

Embodiment 4 provides the composition of any one of embodiment 1-3, and wherein component carbon fibers include a kind of or more Kind carbon fiber.

Embodiment 5 provides the composition of any one of embodiment 2-4, wherein the surface activated includes about 0.05 former The nucleophilic group of sub- concentration % to about 20 atomic concentration %.

Embodiment 6 provides the composition of any one of embodiment 1-5, and wherein polycarbonate component includes copolymerization Object.

Embodiment 7 provides the composition of any one of embodiment 1-6, and wherein polycarbonate component also includes poly- carbon Acid ester copolymer, it includes the repetitive units for being derived from bisphenol derivative, and repetitive unit is each independently random, block Or alternate configurations.

Embodiment 8 provides the composition of embodiment 7, and wherein electrophilic side chain includes carbonyl group.

Embodiment 9 provides the composition of embodiment 8, and wherein carbonyl group is selected from by ester, carboxylic acid and combinations thereof group At group.

Embodiment 10 provides the composition of any one of embodiment 7-9, wherein including the repetition of electrophilic side chain Unit has a structure that

Wherein, R¹It is the aryl group comprising electrophilic side chain.

Embodiment 11 provides the composition of embodiment 10, and wherein aryl group includes phenyl group.

Embodiment 12 provides the composition of embodiment 11, wherein R¹Between in copolymer chain, adjacent or contraposition Replace.

Embodiment 13 provides the composition of any one of embodiment 10-12, wherein R¹It has a structure that

Wherein each R²Independently selected from:

Wherein at least one R²It is ester, and

Wherein R³It is (C₁-C₁₀) alkyl.

Embodiment 14 provides the composition of embodiment 13, wherein comprising electrophilic side chain repetitive unit have with Flowering structure:

Embodiment 15 provides the composition of embodiment 14, wherein R³It is (C₁-C₄) alkyl.

Embodiment 16 provides the composition of embodiment 15, wherein R³Select free methyl, ethyl, propyl, isopropyl, The group of isobutyl group, normal-butyl, sec-butyl, tert-butyl and their combination composition.

Embodiment 17 provides the composition of embodiment 16, wherein comprising electrophilic side chain repetitive unit have with Flowering structure:

Embodiment 18 provides the composition of any one of embodiment 16 or 17, and wherein repetitive unit includes following knot Structure:

Embodiment 19 provides the composition of any one of embodiment 7-18, wherein the repetition of Copolycarbonate Unit is random configuration.

Embodiment 20 provides the composition of any one of embodiment 7-19, and wherein repetitive unit derived from bis-phenol is The about 50mol% to about 99mol% of Copolycarbonate.

Embodiment 21 provides the composition of embodiment 20, and wherein repetitive unit derived from bis-phenol is total for polycarbonate The about 70mol% to about 99mol% of polymers.

Embodiment 22 provides the composition of any one of embodiment 7-21, wherein the repetition containing electrophilic side group Unit is the about 0.2mol% to about 50mol% of Copolycarbonate.

Embodiment 23 provides the composition of embodiment 22, wherein the repetitive unit containing electrophilic side group is poly- carbon The about 0.2mol% to about 20mol% of acid ester copolymer.

Embodiment 24 provides the composition of embodiment 23, wherein the repetitive unit containing electrophilic side group is poly- carbon The about 0.2mol% to about 9mol% of acid ester copolymer.

Embodiment 25 provides the composition of any one of embodiment 7-24, and wherein repetitive unit derived from bis-phenol selects It is bis- from bis- (4- hydroxy phenyl) methane of 1,1-, bis- (4- hydroxy phenyl) ethane of 1,1-, bis- (4- hydroxy phenyl) butane of 2,2-, 2,2- Bis- (4- hydroxy phenyl) propane of (4- hydroxy phenyl) octane, 1,1-, bis- (4- the hydroxy phenyl)-normal butanes of 1,1-, bis- (the 4- hydroxyls of 2,2- Base -1- aminomethyl phenyl) propane, 4,4 '-dihydroxybiphenyls, bis- (4- hydroxy phenyl) methane, bis- (4- hydroxy phenyl) diphenylmethyls Bis- (4- hydroxy phenyl) ethane of alkane, 1,2-, bis- (4- the hydroxy phenyl) -1- diphenylphosphino ethanes of 1,1-, 2- (4- hydroxy phenyl) -2- (3- Hydroxy phenyl) propane, bis- (4- hydroxy phenyl) phenylmethanes, bis- (hydroxy phenyl) pentamethylene of 1,1-, bis- (the 4- hydroxy benzenes of 1,1- Base) hexamethylene, bis- (4- hydroxy phenyl) isobutenes of 1,1-, bis- (4- hydroxy phenyl) cyclododecanes of 1,1-, the bis- (4- of trans- -2,3- Hydroxy phenyl) -2- butylene, bis- (4- hydroxy phenyl) adamantane of 2,2-, (bis- (4- hydroxy phenyl) toluene of α, α ' -, bis- (4- hydroxyls Phenyl) acetonitrile, bis- (4- hydroxy phenyl) ethylene of the chloro- 2,2- of 1,1- bis-, the bromo- 2,2- of 1,1- bis- bis- (4- hydroxy phenyl) ethylene, 3, Bis- (4- the hydroxy phenyl) -2- butanone of 3-, bis- (4- the hydroxy phenyl) -1,6- acetyl butyryls of 1,6-, bis- (4- hydroxy phenyl) ethers of ethylene glycol, Bis- (4- hydroxy phenyl) ethers, bis- (4- hydroxy phenyl) thioethers, bis- (4- hydroxy phenyl) sulfoxides, bis- (4- hydroxy phenyl) sulfones, 9,9- Bis- (4- hydroxy phenyl) fluorenes, 2- phenyl -3,3- pairs-(4- hydroxy phenyl) phthalimidine (PPPBP), the bis- (4- hydroxyl -3- of 2,2- Bromophenyl) propane, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, 2,2- bis- (3- ethyl -4- hydroxy phenyl) propane, 2,2- Bis- (3- isopropyl -4- hydroxy phenyl) propane of bis- (3- n-propyl -4- hydroxy phenyl) propane, 2,2-, bis- (the 3- sec-butyls-of 2,2- 4- hydroxy phenyl) propane, bis- (3- tert-butyl-hydroxy phenyl) propane of 2,2-, bis- (the 3- cyclohexyl -4- hydroxy phenyls) third of 2,2- Bis- (3- allyl -4- hydroxy phenyl) propane of alkane, 2,2-, 2,2- bis- (3- methoxyl group -4- hydroxy phenyl) propane, the bis- (4- of 2,2- Hydroxy phenyl) hexafluoropropane, bis- (5- phenoxy group -4- hydroxy phenyl) ethylene of the chloro- 2,2- of 1,1- bis-, double-(4- hydroxy phenyl) two Phenylmethane), bis- (4- hydroxy diphenyl) methane, 2,2- bis- (4- hydroxyl -3- isopropyl-phenyl) propane, 5,5 '-(1- methyl Ethylidene)-bis- [1,1 '-(double phenyl) -2- alcohol] propane, 1,1- bis- (4- hydroxy phenyl) -3,3,5- trimethyl-cyclohexanes, 1, Bis- (4- the hydroxy phenyl)-hexamethylenes of 1-, bis- (4- hydroxy phenyl) phthalimidines of 2- phenyl -3,3'- and their combination.

Embodiment 26 provides the composition of embodiment 25, wherein the repetitive unit comprising electrophilic side chain is by containing There is the monomer of monofunctional hydroxyl to be formed by end group.

Embodiment 27 provides the composition of any one of embodiment 25 or 26, wherein repetitive unit derived from bis-phenol It is bisphenol-A (bis- (4- hydroxy phenyl) propane of 2,2-).

Embodiment 28 provides the composition of any one of embodiment 7-27, wherein the repetition containing electrophilic side group Unit can be formed by ethyl -3,5- dihydroxy-benzoic acid ester.

Embodiment 29 provides the composition of any one of embodiment 7-28, wherein Copolycarbonate have with Flowering structure:

Embodiment 30 provides the composition of any one of embodiment 7-29, wherein about 0mol% to about 100mol% The repetitive unit comprising electrophilic side chain be crosslinking.

Embodiment 31 provides the composition of any one of embodiment 7-30, wherein about 5% to about 95% includes The repetitive unit of electrophilic side chain is crosslinking.

Embodiment 32 provides the composition of any one of embodiment 7-31, wherein about 30% to about 95% includes The repetitive unit of electrophilic side chain is crosslinking.

Embodiment 33 provides the composition of any one of embodiment 7-32, wherein about 60% to about 95% includes The repetitive unit of electrophilic side chain is crosslinking.

Embodiment 34 provides the composition of any one of embodiment 7-33, wherein about 70% to about 95% includes The repetitive unit of electrophilic side chain is crosslinking.

Embodiment 35 provides the composition of any one of embodiment 30-34, wherein crosslinking is intermolecular cross-linking.

Embodiment 36 provides the composition of any one of embodiment 30-35, wherein crosslinking is intramolecular crosslinking.

Embodiment 37 provides the composition of any one of embodiment 1-36, and wherein component carbon fibers are composition About 1wt% to about 70wt%.

Embodiment 38 provides the composition of any one of embodiment 1-37, and wherein component carbon fibers are composition About 15wt% to about 60wt%.

Embodiment 39 provides the composition of any one of embodiment 1-38, wherein component carbon fibers and polycarbonate Component is directly contacted in interface.

Embodiment 40 provides the composition of any one of embodiment 7-39, and also includes:

The second polycarbonate component without electrophilic side chain.

Embodiment 41 provides the composition of any one of embodiment 39 or 40, and also includes:

Interface between second polycarbonate component and polycarbonate component.

Embodiment 42 provides the composition of any one of embodiment 1-41, also comprising phosphor-containing flame-proof agent addition agent, The fire retardant or their mixture of halogen-containing flame retardant, metal hydroxide-containing.

Embodiment 43 provides the composition of embodiment 42, wherein flame-retardant additive be include in following at least one The phosphonium flame retardant of kind: organic phosphorus compound, triaryl phosphate, phosphite ester (salt), phosphonate ester (salt), polyphosphate (salt), polyphosphate (salt), polyphosphonates (salt) and phosphinate (salt).

Embodiment 44, which is provided, is formed by composite material by the composition of any one of embodiment 1-43, wherein boundary Bread is contained between the surface of the activation of polycarbonate component and component carbon fibers and is formed by covalent bond.

Embodiment 45 provides the composite material of embodiment 44, and wherein covalent bond can be in the activation of component carbon fibers Surface and polycarbonate component electrophilic side chain between formed.

Embodiment 46 provides the composite material of embodiment 45, wherein the electrophilic side chain of about 1% to about 100% is total Valence link is bonded to the surface of the activation of component carbon fibers.

Embodiment 47 provides the composite material of any one of embodiment 45 or 46, wherein about 50% to about 100% Electrophilic side chain be covalently bound to component carbon fibers activation surface.

Embodiment 48 provides the composite material of any one of embodiment 45-47, wherein about 75% to about 100% Electrophilic side chain is covalently bound to the surface of the activation of component carbon fibers.

Embodiment 49 provides the composite material of any one of embodiment 44-48, and wherein material is cured compound Material.

Embodiment 50 provides the composite material formed by the composition of any one of embodiment 1-49, median surface It include the ionic bond formed between polycarbonate component and component carbon fibers.

Embodiment 51 provides the composite material formed by the composition of any one of embodiment 1-50, median surface It include the hydrogen bond formed between polycarbonate component and component carbon fibers.

Embodiment 52 provides the composite material of embodiment 51, wherein can be in the electrophilic side of polycarbonate component Hydrogen bond is formed between the surface of the activation of chain and component carbon fibers.

Embodiment 53 provides the composite material formed by the composition of any one of embodiment 1-52, median surface Include the Van der Waals force between polycarbonate component and component carbon fibers.

Embodiment 54 provides the composite material of embodiment 53, and wherein Van der Waals force is in the electrophilic of polycarbonate component Between the surface of the activation of sub- side chain and component carbon fibers.

Embodiment 55 provides the composite material formed by the composition of any one of embodiment 1-54, median surface Include the mechanical connection between polycarbonate component and component carbon fibers.

Embodiment 56 provides the composite material of embodiment 55, and wherein polycarbonate component at least partly winds carbon fiber Tie up component.

Embodiment 57 provides the composite material of any one of embodiment 30-56, wherein the anti-flammability of composite material Greater than with intermolecular or intramolecular crosslinking the corresponding composite material more less than composite material.

Embodiment 58 provides the method to form composite material comprising:

The composition of embodiment 1 is contacted with mold；

Heating mould；With

Pressure is applied to mold；

Composite material can wherein be formed.

Embodiment 59 provides the method for embodiment 58, and wherein heating mould includes the composition for making embodiment 1 Solidification.

Embodiment 60 provides the method for any one of embodiment 58 or 59, wherein mold is heated above poly- carbon The temperature of the melting temperature of acid esters component.

Embodiment 61 provides the method for any one of embodiment 58-60, wherein mold is heated to about 100 DEG C extremely Temperature in the range of about 350 DEG C.

Embodiment 62 provides the method for any one of embodiment 58-61, wherein mold is heated to about 200 DEG C extremely Temperature in the range of about 350 DEG C.

Embodiment 63 provides the method for any one of embodiment 58-62, wherein mold is heated about 1 minute to about 60 minutes.

Embodiment 64 provides the method for any one of embodiment 58-63, wherein mold is heated about 1 minute to about 30 minutes.

Embodiment 65 provides the method for any one of embodiment 58-64, wherein mold is heated about 1 minute to about 15 minutes.

Embodiment 66 provides the method for any one of embodiment 58-65, and further includes applying to press to composition Power.

Embodiment 67 provides the method for embodiment 66, and wherein pressure limit is about 0.5 ton to about 4 tons.

Embodiment 68 provides the method for any one of embodiment 66 or 67, and wherein pressure limit is about 1 ton to about 2 Ton.

In entire this document, in a flexible way the value indicated using range format should be interpreted as not only to include as model The numerical value that limitation is clearly enumerated is enclosed, but also including all single numbers covered within the scope of this or subrange, as clear List each numerical value and subrange.For example, " about 0.1% to about 5% " or the range of " about 0.1% to 5% " are interpreted as It not only include about 0.1% to about 5%, but also including the single value in specified range (for example, 1%, 2%, 3% and And subrange (for example, 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) 4%).Unless otherwise stated, otherwise State that " about X to Y " and " about X to about Y " has identical meanings.Similarly, unless otherwise stated, otherwise " about X, Y or about Z " is stated There are identical meanings with " about X, about Y or about Z ".

In the document, unless clearly, otherwise term "one", "an" or "the" be used to include one It is a or more than one.Unless otherwise stated, otherwise term "or" is used to indicate non-exclusive "or".Statement is " at least one in A and B It is a " with " A, B or A and B " have identical meanings.In addition, it will be appreciated that the used herein and expression way that does not in addition define or Term is only for purposes of illustration rather than limits.Any use of division header is intended to help reading documents, without answering It is interpreted as limiting；Information related with division header can occur within the specific part or in addition.

In method described herein, except when clearly enumerating outside time or operation order, without departing substantially from original of the invention In the case where reason, it can implement to operate in any order.In addition, unless specific claim language tell about them should be individually real Outside applying, specified operation can be implemented simultaneously.For example, can be carried out simultaneously in single operation advocated implementation X movement and The movement of the implementation Y advocated, and gained process will belong in the literal scope of advocated process.

As used herein term " about " can permit a degree of change of several value or ranges, for example, designated value or Within the 10% of specified range limitation, within 5% or within 1%, and the value or range including exact meaning.

As used herein term " substantially " refer to it is most of or mainly, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99% or at least about 99.999% or with On or 100%.

Term as used herein " alkyl " refers to 1 to 40 carbon atom, 1 to about 20 carbon atom, 1 to 12 carbon Alternatively, in some embodiments, the substituted or unsubstituted straight chain and branched alkyl group and cycloalkanes of 1 to 8 carbon atom Base group.The example of straight chained alkyl includes having those of 1 to 8 carbon atom, such as methyl, ethyl, n-propyl, normal-butyl, just Amyl, n-hexyl, n-heptyl and n-octyl group.The example of branched alkyl group includes but is not limited to isopropyl, isobutyl group, secondary Butyl, tert-butyl, neopentyl, isopentyl and 2,2- dimethylpropyl group.As it is used herein, term " alkyl " includes nalka The alkyl of base, isoalkyl and anteiso- alkyl group and other branched forms.Representative substituted alkyl group can be appointed The substitution of group listed by what this paper is one or many, for example, amino, hydroxyl, cyano, carboxyl, nitro, sulfenyl, alkoxy and halogen Group.

As used herein term " naphthenic base " refers to substitution and unsubstituted cyclic alkyl radical, such as, but not limited to, ring Propyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and cyclooctyl group.In some embodiments, naphthenic base can have 3 To about 8-12 ring members, however in other embodiments, the number of ring carbon atom is in the range of 3 to 4,5,6 or 7.? In some embodiments, naphthenic base can have 3 to 6 carbon atom (C₃-C₆).Naphthenic base further includes polycyclic naphthene base group, such as But it is unlimited) norborny, adamantyl, bornyl, amphene base, different amphene base and carene base and condensed ring, such as, but not limited to, ten Hydrogen naphthalene etc..

As used herein term " aryl " refers in ring without heteroatomic substitution and unsubstituted cyclophane alkyl Group.Therefore, aryl group includes but is not limited to phenyl, azulenyl and trialkenyl (heptalenyl), diphenyl, indacene between heptan Base (indacenyl), fluorenyl, phenanthryl, triphenylene (triphenylenyl), pyrenyl, aphthacene base (naphthacenyl), Qu Ji, biphenylene (biphenylenyl), anthryl and naphthyl group.In some embodiments, aryl group is in group Contain about 6 to about 14 carbon in loop section.As herein defined, aryl group can be unsubstituted or substituted.It represents Property substituted aryl group can be it is mono-substituted or replace more than once, such as, but not limited to, 2-, 3- of phenyl ring, 4-, Any one or more of 5- or 6- substitution phenyl or any one or more of its 2- or 8- substitution Naphthalene.

Unless otherwise stated, as used herein term " halogenated ", " halogen " or " halide " itself or conduct A part of another substituent group indicates fluorine, chlorine, bromine or iodine atom.

As used herein term " alkoxy " refers to as herein defined, is connected to alkyl, including naphthenic base base The oxygen atom of group.The example of unbranched alkoxy include but is not limited to methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, oneself Oxygroup etc..The example of branched alkoxy includes but is not limited to isopropoxy, sec-butoxy, tert-butoxy, isoamoxy, dissident's oxygen Base etc..The example of cyclic alkoxy includes but is not limited to cyclopropyl oxygroup, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy etc..Alkoxy It may include be bonded to oxygen atom about 1 to about 12, about 1 to about 20 or about 1 to about 40 carbon atom, and can also include double Key or three keys, and can also include hetero atom.For example, allyloxy group or methoxyethoxy group are also in this paper meaning Alkoxy, such as the methylenedioxy in two adjacent atoms in the structure simultaneously substituted background.

As used herein term " arlydene " refers to by removing divalent derived from two hydrogen atoms from aromatic hydrocarbons Group is that have 6 to 18 carbon atoms, 10 to 18 carbon atoms, 12 to 18 carbon atoms, 6 to about 10 carbon atoms or 6 To the cycloaromatics of 8 carbon atoms.(C₆-C₁₈) example of arylene group includes:

Wherein wave represents and such as-(C₁-C₆The tie point of)-alkylidene.

As used herein term " aryl alkyl " refers to the wherein hydrogen of alkyl or carbon key by virtue as herein defined The alkyl as herein defined that the key of base replaces.

As used herein term " heteroaryl " refers to the aromatic cycle compound containing 5 or more ring members, ring One or more of member is hetero atom, such as, but not limited to, N, O and S；For example, heteroaryl ring can have 5 to about 8-12 Ring members.

As used herein term " substituted ", which refers to, can replace or replace the group to molecule.The reality of substituent group Example includes but is not limited to halogen (for example, F, Cl, Br and I)；Such as hydroxyl group, alkoxy base, aryloxy group, aralkoxy Group, oxo (carbonyl) group group in oxygen atom, carboxylic group, including carboxylic acid, carboxylate and carboxylate；Such as mercapto Group, alkyl and aryl thioether, sulfoxide group group, sulfuryl group, sulphonyl groups and sulfoamido group group in Sulphur atom；As amine, azanol, nitrile, nitro, N- oxide, hydrazides, azide and enamine group in nitrogen-atoms；With it is more Other hetero atoms in the other groups of kind.The non-limiting example of substituent group includes F, Cl, Br, I, OR, OC (O) N (R)₂、CN、 NO、NO₂、ONO₂, azido, CF₃、OCF₃, R, O (oxygen), S (sulphur), C (O), S (O), methylene-dioxy, ethylenedioxy, N (R)₂、SR、SOR、SO₂R、SO₂N(R)₂、SO₃R、C(O)R、C(O)C(O)R、C(O)CH₂C(O)R、C(S)R、C(O)OR、OC(O) R、C(O)N(R)₂、OC(O)N(R)₂、C(S)N(R)₂、(CH₂)_0-2N(R)C(O)R、(CH₂)_0-2N(R)N(R)₂、N(R)N(R)C(O) R、N(R)N(R)C(O)OR、N(R)N(R)CON(R)₂、N(R)SO₂R、N(R)SO₂N(R)₂、N(R)C(O)OR、N(R)C(O)R、N (R)C(S)R、N(R)C(O)N(R)₂、N(R)C(S)N(R)₂, N (COR) COR, N (OR) R, C (=NH) N (R)₂、C(O)N(OR)R With C (=NOR) R, wherein R can be hydrogen or the part based on carbon；For example, R can be hydrogen, alkyl, acyl group, naphthenic base, aryl, Aralkyl, heterocycle, heteroaryl or heteroarylalkyl；Or wherein it is bonded to nitrogen-atoms or two R groups of adjacent nitrogen atom can To be formed together heterocyclic group with nitrogen-atoms.As used herein term " acyl group " refers to the group containing carbonyl moiety, Middle group is bonded by carbonylic carbon atom.

As used herein term " aralkyl " refers to the wherein hydrogen of alkyl or carbon key by aryl as herein defined Key replace alkyl as herein defined.Representative aralkyl includes benzyl and phenethyl, and condensed (naphthenic base virtue Base) alkyl, such as 4- ethyl-indanyl.

As used herein term " heterocycle " refers to containing there are three or the fragrance and non-aromatic ring of above ring members Compound, one or more of ring members are hetero atom, such as (but not limited to) N, O and S.

As used herein term " heteroaryl " refers to the aromatic cycle compound containing 5 or more ring members, ring One or more of member is hetero atom, such as, but not limited to, N, O and S；For example, heteroaryl ring can have 5 to about 8-12 Ring members.Heteroaryl groups are multiple heterocycles with aromatic series electronic structure.

As used herein term " heteroarylalkyl " refers to the wherein hydrogen of alkyl or carbon key by miscellaneous as herein defined The alkyl group as herein defined that the key of aryl group replaces.

As used herein term " number-average molecular weight " (M_n) refer to that the conventional of the molecular weight of individual molecule is calculated in sample Art average value.Its total weight for being defined as all molecules in sample divided by molecule in sample sum.Experimentally, pass through analysis It is divided into molecular weight M_iN_iThe sample of the molecular weight fractions of the substance i of a molecule, and pass through formula M_n=Σ M_in_i/Σn_iReally Determine M_n.A variety of well known methods, including gel permeation chromatography, spectrophotometric end-group analysis and osmometry can be passed through Method measures M_n.If do not indicated, the molecular weight of polymer provided in this article is number-average molecular weight.

Term " weight average molecular weight " (M_w) it is equal to Σ M_i ²n_i/ΣM_in_i, wherein n_iIt is molecular weight M_iMolecule number.More In a embodiment, light scattering, neutron small angle scattering, X-ray scattering and sinking speed can be used to determine weight average molecular weight.

As used herein term " solidification ", which refers to, to be exposed to any type of radiation, heats or be subjected to cause hard Change or viscosity is raised physically or chemically reacts.For example, flowable thermoplastic material cures can be made by being allowed to cool, from And make material hardening.As another example, flowable thermosetting material can be made to solidify by any suitable method, including It heats or is otherwise exposed to radiate, to make material hardening.

Claims

1. a kind of composition, includes:

Polycarbonate component includes the repetitive unit containing electrophilic side chain；

Component carbon fibers, the surface comprising activation, wherein the surface of the activation includes nucleophilic group；With

Interface between the polycarbonate component and the component carbon fibers.

2. composition according to claim 1, wherein the nucleophilic group selects free hydroxyl group, carboxylic group, amino The group of group and their combination composition.

3. according to claim 1 or composition as claimed in claim 2, wherein the component carbon fibers include one or more Carbon fiber.

4. composition according to any one of claim 1 to 3, wherein the polycarbonate component also includes poly- carbonic acid Ester copolymer, the Copolycarbonate include the repetitive unit derived from bisphenol derivative, and the repetitive unit is respectively only It is on the spot random, block or alternate configurations.

5. composition according to any one of claim 1 to 4, wherein the electrophilic side chain includes carbonyl group.

6. composition according to claim 4, wherein the repetitive unit containing electrophilic side chain has following knot Structure:

Wherein, R¹It is the aryl group containing electrophilic side chain.

7. composition according to claim 6, wherein the aryl group includes phenyl group.

8. composition according to claim 7, wherein R¹Meta position, ortho position or contraposition in the main chain of the copolymer take Generation.

9. composition according to claim 6, wherein R¹It has a structure that

Wherein each R²Independently selected from:

With-H,

Wherein at least one R²It is ester, and

Wherein R³It is (C₁-C₁₀) alkyl.

10. composition according to claim 9, wherein the repetitive unit containing electrophilic side chain has following knot Structure:

11. composition according to claim 10, wherein R³It is (C₁-C₄) alkyl.

12. composition according to claim 11, wherein R³In the group being made up of: methyl, ethyl, propyl, Isopropyl, isobutyl group, normal-butyl, sec-butyl, tert-butyl and combinations thereof.

13. composition according to claim 12, wherein the repetitive unit containing electrophilic side chain has following knot Structure:

14. composition according to claim 13, wherein the repetitive unit includes with flowering structure:

15. composition according to claim 4, wherein the repetitive unit of the Copolycarbonate is random configuration.

16. composition according to claim 4, wherein the Copolycarbonate has a structure that

17. a kind of method for forming composite material, comprising:

Contact composition described in claim 1 with mold；

Heat the mold；With

Pressure is applied to the mold；

Wherein form the composite material.

18. according to the method for claim 17, wherein heating the mold includes making composition described in claim 1 Solidification.

19. according to the method for claim 18, wherein the mold to be heated to about within the scope of 100 DEG C to about 350 DEG C Temperature.

20. according to the method for claim 18, wherein the mold to be heated to about within the scope of 200 DEG C to about 350 DEG C Temperature.